DE502005008522C5 - Use of polyolefin waxes in hotmelt compositions - Google Patents

Use of polyolefin waxes in hotmelt compositions

Info

Publication number
DE502005008522C5
DE502005008522C5 DE502005008522.1T DE502005008522T DE502005008522C5 DE 502005008522 C5 DE502005008522 C5 DE 502005008522C5 DE 502005008522 T DE502005008522 T DE 502005008522T DE 502005008522 C5 DE502005008522 C5 DE 502005008522C5
Authority
DE
Germany
Prior art keywords
hot melt
waxes
polyolefin waxes
melt compositions
characterized
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
DE502005008522.1T
Other languages
German (de)
Other versions
DE502005008522D1 (en
Inventor
Sebastijan Bach
Hans-Friedrich Herrmann
Gerd Hohner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Produkte Deutschland GmbH
Original Assignee
Clariant Produkte Deutschland GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to DE102004048536 priority Critical
Priority to DE102004048536A priority patent/DE102004048536B4/en
Application filed by Clariant Produkte Deutschland GmbH filed Critical Clariant Produkte Deutschland GmbH
Publication of DE502005008522D1 publication Critical patent/DE502005008522D1/en
Application granted granted Critical
Publication of DE502005008522C5 publication Critical patent/DE502005008522C5/en
Application status is Active legal-status Critical
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JAdhesives; non-mechanical aspects of adhesive processes in general; adhesive processes not provided for elsewhere; use of material as adhesives
    • C09J123/00Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/10Homopolymers or copolymers of propene
    • C09J123/12Polypropene
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JAdhesives; non-mechanical aspects of adhesive processes in general; adhesive processes not provided for elsewhere; use of material as adhesives
    • C09J123/00Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/10Homopolymers or copolymers of propene
    • C09J123/14Copolymers of propene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00Polymer mixtures characterised by way of preparation
    • C08L2314/06Metallocene or single site catalysts
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C08L2666/06Homopolymers or copolymers of unsaturated hydrocarbons; Derivatives thereof

Abstract

Hot melt compositions comprising one or more polyolefin waxes prepared by means of metallocene catalysts, a dropping or softening point ring / ball between 80 and 165 ° C, a melt viscosity, measured at a temperature of 170 ° C, between 20 and 40,000 mPa · s and a glass transition temperature of at most -10 ° C, characterized in that the polyolefin waxes are present in a proportion by weight of greater than or equal to 50 wt .-% in the hot melt compositions, wherein in the hot melt compositions, the one or more polyolefin waxes are copolymer waxes of propylene and ethylene and the content of structural units derived from propylene in the copolymer waxes is from 70 to 99.9% by weight.

Description

  • The invention relates to hot melt compositions containing polyolefin waxes prepared with metallocene catalysts.
  • Hot melt compounds or hot melts are thermoplastic materials which are solid at ambient temperature and, in the molten state, are applied in layers to suitable substrate surfaces and exert different functions there after solidification. They are preferably based on resins, waxes, thermoplastics and elastomers and optionally contain additives of fillers, pigments and additives such as stabilizers etc.
  • For example, hotmelt compositions can be used as solvent-free adhesives for bonding. Such hot melt adhesives are due to their versatile advantages increasingly u. a. used in the packaging, furniture, textile and footwear industries as an economical and environmentally friendly alternative to traditional solvent-based adhesives. Components of conventional hot-melt adhesive formulations are polar or non-polar polymers - usually ethylene-vinyl acetate copolymers - resins and waxes.
  • In WO 2004/046214 Polypropylene polymers and polypropylene copolymers are presented, which can also be prepared using metallocene catalysts, but which differ from the claimed products and have different properties. Out US 2002/0007033 For example, copolymers which are said to have good adhesion properties are also known, but the hot melt compositions according to the invention containing specific propylene-ethylene copolymers are not disclosed. US 2002/0019507 describes polymers which differ from the particular propylene-ethylene copolymers used according to the invention and lead to other properties.
  • The polar or non-polar polymers serve as builder. They ensure the cohesive cohesion of the adhesive and at the same time contribute to the adhesion to the substrate. The addition of resin improves the adhesion effect and may optionally exert a compatibilizing effect on the various adhesive components. Waxes are used for modification in proportions, based on the hotmelt adhesive compositions of usually less than 10 wt .-%. They regulate important physical properties of the adhesives, such as hardness, melt viscosity and softening point, and their effect on open time, adhesion, cohesion, etc. decisively influences the application-technical behavior. In wax use amounts of more than 10 wt .-% hitherto has generally been found to deteriorate the properties, in particular a reduction in the bond strength of the hot melt adhesive.
  • Hot melt compositions are still used in road construction as a thermoplastic binder for producing traffic-guiding visual signs such. B. "zebra crossings" at pedestrian crossings, middle or boundary lines or other signaling information to control the flow of traffic. The binders used for this purpose may contain, in addition to waxes, thermoplastics, resins and plasticizers. For use in road marking, these binders are usually filled with fillers such as sand or lime, pigments such as titanium dioxide and light-reflecting additives, eg. B. mixed glass beads.
  • In the past, macro- and microcrystalline paraffin waxes, Fischer-Tropsch waxes and polyolefin waxes have been used as waxes in hotmelt compositions. Polyolefin waxes are here understood to mean low molecular weight polyolefins in the molar mass range between about 500 and 20,000 g / mol (number average molar mass M n ) and MFR values, measured according to ASTM D 1238-01, of greater than 3000 g / 10 min.
  • Polyolefin waxes can be prepared by thermal degradation of branched high polymer polyolefin plastics or by direct polymerization of olefins. For example, high-pressure technologies are suitable as the polymerization process, the olefins, generally ethylene, being reacted at high pressures and temperatures to branched waxes in a radical manner, besides low-pressure or Ziegler processes in which ethylene and / or higher 1-olefins are used organometallic catalysts are polymerized at relatively lower pressures and temperatures.
  • As a variant of the low-pressure process, a procedure has recently become known in which metallocene catalysts are used as organometallic catalysts. The latter contain titanium, zirconium or hafnium atoms as active species and are usually used in combination with cocatalysts, eg. As organoaluminum or boron compounds, preferably aluminoxane compounds used. If required, the polymerization is carried out in the presence of hydrogen as molecular weight regulator. Metallocene processes are characterized by the fact that compared to older Zieglertechnologie waxes with tighter Molar mass distribution, uniform comonomer incorporation, lower melting points and higher catalyst efficiency can be obtained.
  • Surprisingly, it has now been found that hot melt compositions containing polyolefin waxes prepared with the aid of metallocene catalysts have a dropping or softening point ring / sphere between 80 and 165 ° C., a melt viscosity, measured at a temperature of 170 ° C., between 20 and 40,000 mPa · s and a glass transition temperature of -10 ° C maximum, are particularly suitable as a hot melt adhesive. In this case, the polyolefin waxes are in a proportion by weight of greater than or equal to 50 wt .-% in the hot melt compositions, wherein in the hot melt compositions, the one or more polyolefin waxes are copolymer waxes of propylene and ethylene, and the content of structural units resulting from propylene in the copolymer waxes of 70 to 99.9 wt .-% is.
  • Such hot melt adhesives have superior adhesives (adhesion to substrate) and cold flexibility properties.
  • Furthermore, it has been found that the said hotmelt compositions are excellently suitable as constituents of road marking compounds. In particular, such marking compositions have improved adhesion to the road.
  • The invention therefore relates to hot melt compositions containing one or more polyolefin waxes prepared with the aid of metallocene catalysts, a dropping or softening point ring / ball between 80 and 165 ° C, a melt viscosity, measured at a temperature of 170 ° C, between 20 and 40000 mPa · s and a glass transition temperature of at most -10 ° C, wherein the polyolefin waxes are in a proportion by weight of greater than or equal to 50 wt .-% in the hot melt compositions, wherein in the hot melt compositions, the one or more polyolefin waxes copolymer waxes are propylene and ethylene, and the content of structural units resulting from propylene in the copolymer waxes is from 70 to 99.9% by weight
  • Preferably, the polyolefin waxes contained in the hotmelt compositions according to the invention have a dropping or softening point ring / ball between 90 and 160 ° C, a melt viscosity, measured at a temperature of 170 ° C, between 50 and 30,000 mPa · s and a glass transition temperature of -20 maximum ° C on.
  • The polyolefin waxes contained in the hotmelt compositions according to the invention preferably have a number average molecular weight M n of between 500 and 20,000 g / mol, more preferably between 800 and 10,000 g / mol and especially preferably between 1,000 and 5,000 g / mol and preferably a weight average molecular weight M w of between 1,000 and 40,000 g / mol, more preferably between 1,600 and 30,000 g / mol, and most preferably between 2,000 and 20,000 g / mol.
  • As in the hot melt compositions of the invention contained polyolefin waxes are copolymers of propylene with ethylene in question. The copolymers are preferably 70 to 99.9% and more preferably 80 to 99% by weight of an olefin type. Also suitable are copolymers of propylene with 0.1 to 30, preferably 1 to 20 wt .-% of ethylene.
  • In one embodiment of the invention, the polyolefin waxes contained in the hotmelt compositions are copolymer waxes of propylene and ethylene, wherein the content of structural units resulting from propylene in the copolymer waxes is from 70 to 99.9% by weight. To prepare these copolymer waxes, the mentioned 1-alkenes can be used.
  • The olefin homo- and copolymer waxes used in the hotmelt compositions may be polar modified.
  • The novel hot melt compositions may additionally contain polyolefin plastics, resins, waxes, plasticizers, polar or nonpolar polymers, pigments, fillers, stabilizers and / or antioxidants.
  • Metallocene compounds of the formula I are used for the preparation of the polyolefin waxes used according to the invention.
    Figure DE502005008522C5_0001
  • This formula also includes compounds of the formula Ia,
    Figure DE502005008522C5_0002
    the formula Ib
    Figure DE502005008522C5_0003
    and the formula Ic
    Figure DE502005008522C5_0004
  • In formulas I, Ia and Ib, M 1 is a Group IVb, Vb or VIb metal of the Periodic Table, for example, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, preferably titanium, zirconium, hafnium.
  • R 1 and R 2 are the same or different and represent a hydrogen atom, a
    C 1 -C 10 -, preferably C 1 -C 3 -alkyl group, in particular methyl, a C 1 -C 10 -, preferably C 1 -C 3 -alkoxy group, a C 6 -C 10 -, preferably C 6 -C 8 -Arylgruppe, a C 6 -C 10 -, preferably C 6 -C 8 -aryloxy group, a C 2 -C 10 -, preferably C 2 -C 4 alkenyl group, a C 7 -C 40 -, preferably C 7 -C 10 -Arylalkylgruppe, a C 7 -C 40 -, preferably C 7 -C 12 alkylaryl group, a C 8 -C 40 -, preferably C 8 -C 12 -Arylalkenylgruppe or a halogen, preferably chlorine atom.
  • R 3 and R 4 are identical or different and denote a mononuclear or polynuclear hydrocarbon radical which can form a sandwich structure with the central atom M 1 . R 3 and R 4 are preferably cyclopentadienyl, indenyl, tetrahydroindenyl, benzoindenyl or fluorenyl, it being possible for the basic units to carry additional substituents or to bridge them with one another. In addition, one of the radicals R 3 and R 4 may be a substituted nitrogen atom, wherein R 24 has the meaning of R 17 and is preferably methyl, tert-butyl or cyclohexyl.
  • R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are identical or different and denote a hydrogen atom, a halogen atom, preferably a fluorine, chlorine or bromine atom, a C 1 -C 10 -, preferably C 1 C 4 alkyl group, a C 6 -C 10 , preferably C 6 -C 8 aryl group, a C 1 -C 10 , preferably C 1 -C 3 alkoxy group, an -NR 16 2 -, -SR 16 -
    -OSiR 16 3 , -SiR 16 3 or -PR 16 2 radical, in which R 16 is a C 1 -C 10 -, preferably C 1 -C 3 -alkyl group or C 6 -C 10 -, preferably C 6 - C 8 aryl group or in the case of Si or P-containing radicals is also a halogen atom, preferably chlorine atom or two adjacent radicals R 5 , R 6 , R 7 , R 8 , R 9 or R 10 form with the connecting them
    C atoms form a ring. Particularly preferred ligands are the substituted compounds of the parent compounds cyclopentadienyl, indenyl, tetrahydroindenyl, benzoindenyl or fluorenyl.
  • R is 13
    Figure DE502005008522C5_0005
    = BR 17 , = AlR 17 , -Ge, -Sn, -O-, -S-, = SO, = SO 2 , = NR 17 , = CO, = PR 17 or = P (O) R 17 , wherein R 17 , R 18 and R 19 are the same or different and a hydrogen atom, a halogen atom, preferably a fluorine, chlorine or bromine atom, a C 1 -C 30 , preferably C 1 -C 4 alkyl, especially methyl group , a C 1 -C 10 fluoroalkyl, preferably CF 3 , C 6 -C 10 fluoroaryl, preferably pentafluorophenyl, C 6 -C 10 , preferably C 6 -C 8 aryl, C 1 -C 10 -, preferably C 1 -C 4 -alkoxy, in particular methoxy, a C 2 -C 10 -, preferably C 2 -C 4 -alkenyl, a C 7 -C 40 -, preferably C 7 -C 10 - Aralkyl group, a C 8 -C 40 -, preferably C 8 -C 12 -Arylalkenylgruppe or a
    C 7 -C 40 -, preferably C 7 -C 12 -alkylaryl group, or R 17 and R 18 or R 17 and R 19 each form a ring together with the atoms connecting them.
  • M 2 is silicon, germanium or tin, preferably silicon and germanium. R 13 is preferably = CR 17 R 18 , = SiR 17 R 18 , = GeR 17 R 18 , -O-, -S-, = SO, = PR 17 or = P (O) R 17 .
  • R 11 and R 12 are the same or different and have the meaning given for R 17 . m and n are the same or different and are zero, 1 or 2, preferably zero or 1, where m plus n is zero, 1 or 2, preferably zero or 1.
    R 14 and R 15 have the meaning of R 17 and R 18 .
  • Examples of suitable metallocenes are:
    Bis (1,2,3-trimethyl) zirconium,
    Bis (1,2,4-trimethylcyclopentadienyl) zirconium dichloride,
    Bis (1,2-dimethylcyclopentadienyl) zirconium dichloride,
    Bis (1,3-dimethylcyclopentadienyl) zirconium dichloride,
    Bis (1-methylindenyl) zirconium dichloride,
    Bis (1-n-butyl-3-methyl-cyclopentadienyl) zirconium dichloride,
    Bis (2-methyl-4,6-di-i.propyl-indenyl) zirconium dichloride,
    Bis (2-methylindenyl) zirconium dichloride,
    Bis (4-methylindenyl) zirconium dichloride,
    Bis (5-methylindenyl) zirconium dichloride,
    Bis (alkylcyclopentadienyl) zirconium,
    Bis (alkylindenyl) zirconium,
    Bis (cyclopentadienyl) zirconium,
    (Indenyl) zirconium,
    Bis (methylcyclopentadienyl) zirconium dichloride,
    Bis (n-butylcyclopentadienyl) zirconium dichloride,
    To (octadecylcyclopentadienyl) zirconium,
    Bis (pentamethylcyclopentadienyl) zirconium,
    Bis (trimethylsilyl) zirconium,
    Biscyclopentadienylzirkoniumdibenzyl,
    Biscyclopentadienylzirkoniumdimethyl,
    Bistetrahydroindenylzirkoniumdichlorid,
    Dimethylsilyl-9 fluorenylcyclopentadienylzirkoniumdichlorid,
    Dimethylsilyl-bis-1- (2,3,5-trimethylcyclopentadienyl) zirconium dichloride,
    Dimethylsilyl-bis-1- (2,4-dimethyl-cyclopentadienyl) zirconium dichloride,
    Dimethylsilyl-bis-1- zirconium dichloride (2-methyl-4,5-benzoindenyl)
    Dimethylsilyl-bis-1- (2-methyl-4-ethylindenyl) zirconium dichloride,
    Dimethylsilyl-bis-1- (2-methyl-4-i-propylindenyl) zirconium dichloride,
    Dimethylsilyl-bis-1- (2-methyl-4-phenylindenyl) zirconium dichloride,
    (2-methyl-indenyl) zirconium dichloride dimethylsilyl-bis-1,
    Dimethylsilyl-bis-1- (2-methyltetrahydroindenyl) zirconium dichloride,
    Dimethylsilyl-bis-1-indenylzirkoniumdichlorid,
    Dimethylsilyl-bis-1-indenylzirkoniumdimethyl,
    Dimethylsilyl-bis-1-tetrahydroindenylzirkoniumdichlorid,
    Diphenylmethylene-9-fluorenylcyclopentadienylzirkoniumdichlorid,
    Diphenylsilyl-bis-1-indenylzirkoniumdichlorid,
    Ethylene-bis-1- zirconium dichloride (2-methyl-4,5-benzoindenyl)
    Ethylene-bis-1- (2-methyl-4-phenylindenyl) zirconium dichloride,
    Ethylene-bis-1- (2-methyl-tetrahydroindenyl) zirconium dichloride,
    Ethylene-bis-1- (4,7-dimethyl-indenyl) zirconium dichloride,
    Ethylene-bis-1-indenylzirkoniumdichlorid,
    Ethylene-bis-1-tetrahydroindenylzirkoniumdichlorid,
    Indenyl-cyclopentadienyl zirconium
    Isopropylidene (1-indenyl) (cyclopentadienyl) zirconium dichloride,
    Isopropylidene (9-fluorenyl) (cyclopentadienyl) zirconium dichloride,
    (2-methyl-indenyl) zirconium dichloride phenylmethylsilyl-bis-1-,
    and in each case the alkyl or aryl derivatives of these metallocene dichlorides.
  • To activate the single-center catalyst systems suitable cocatalysts are used. Suitable cocatalysts for metallocenes of the formula I are organoaluminum compounds, in particular alumoxanes or else aluminum-free systems such as R 20 x NH 4 -x BR 21 4 , R 20 x PH 4-x BR 21 4 , R 20 3 CBR 21 4 or BR 21 3 , In these formulas, x is a number from 1 to 4, the radicals R 20 are identical or different, preferably identical, and are C 1 -C 10 -alkyl or C 6 -C 18 -aryl or two radicals R 20 form together with the they join a ring and the radicals R 21 are the same or different, preferably the same, and are C 6 -C 18 -aryl which may be substituted by alkyl, haloalkyl or fluorine. In particular, R 20 is ethyl, propyl, butyl or phenyl and R 21 is phenyl, pentafluorophenyl, 3,5-bis-trifluoromethylphenyl, mesityl, xylyl or tolyl.
  • In addition, a third component is often required to maintain protection of polar catalyst poisons. For this purpose, organoaluminum compound such. As triethylaluminum, tributylaluminum and others and mixtures suitable.
  • Depending on the process, supported single-center catalysts can also be used. Preference is given to catalyst systems in which the residual contents of support material and cocatalyst do not exceed a concentration of 100 ppm in the product.
  • To produce the hotmelt compositions according to the invention, it is possible to use polyolefin metallocene waxes in unmodified or in polar modified form. Polar modified waxes are prepared in a known manner from non-polar raw materials by oxidation with oxygen-containing gases, for example air, or by radical grafting reaction with polar monomers, for example α, β-unsaturated carboxylic acids or derivatives thereof such as acrylic acid, maleic acid or maleic anhydride or unsaturated organosilane compounds such as Trialkoxyvinylsilanen. The polar modification of metallocene polyolefin waxes by oxidation with air is exemplified by EP 0 890 583 For example, the modification by grafting in US-A-5,998,547 or JP 54-145785 described.
  • Another object of the invention is the use of hot melt compositions according to the invention as a hot melt adhesive.
  • The polyolefin waxes are preferably contained in a proportion by weight of greater than or equal to 50 wt .-%, more preferably between 50 and 99 wt .-% and particularly preferably between 60 and 90 wt .-% in the hot melt compositions used as hot melt adhesives. Other possible ingredients are resins, waxes and nonpolar or polar polymers such. As ethylene-vinyl acetate copolymers, atactic poly-α-olefins (APAO), polyisobutylene, styrene-butadiene-styrene block polymers or styrene-isoprene-styrene block polymers, for particularly highly stressed bonds and polyamides or polyesters. As resin components z. As rosins and their derivatives or hydrocarbon resins may be included, as Waxes hydrocarbon waxes such as Fischer-Tropsch paraffins, polyolefin waxes not produced with metallocene catalysts, these being nonpolar or polar modified, for. B. oxidized or grafted with polar monomers such as maleic anhydride, may be. The hot-melt adhesive compositions may additionally contain fillers or auxiliaries, such as plasticizers, pigments and stabilizers, such as antioxidants or light stabilizers.
  • Another object of the invention is the use of hot melt compositions according to the invention as a binder for the production of road markings.
  • The polyolefin waxes are preferably present in the hotmelt compositions used as a binder for the road marking with a weight fraction of between 5 and 99% by weight.
  • In a particularly preferred embodiment of the invention, the polyolefin waxes are contained in the hot melt compositions used as a binder for the road marking with a weight fraction of between 20 and 90% by weight.
  • In a further particularly preferred embodiment of the invention, the polyolefin waxes are contained in the hot melt compositions used as binders for the road marking with a weight fraction of between 50 and 99% by weight.
  • The polyolefin waxes are very particularly preferably contained in the hotmelt compositions used as binders for the road marking, with a proportion by weight of between 60 and 90% by weight.
  • Other possible ingredients are non-polar or polar polymers, resins and waxes of the type described above and plasticizers such. For example, paraffin oil and antioxidants. For use in road marking, the binder is usually with other components such as fillers, for. As sand or lime and pigments such. As titanium dioxide and light-reflecting additives such. B. mixed glass beads.
  • The following examples are intended to illustrate the invention in more detail without, however, limiting it thereto.
  • Examples
  • The melt viscosities were determined in accordance with DIN 53019 using a rotational viscometer, the dropping points in accordance with DIN 51801/2, the softening points ring / ball in accordance with DIN EN 1427 and the glass transition temperatures using differential thermal analysis in accordance with DIN 51700. The molecular weight average M w , the molecular weight average M n and the resulting quotient M w / M n were determined by gel permeation chromatography at 135 ° C in 1,2-dichlorobenzene.
  • The metallocene polyolefin waxes used according to the invention and listed in Table 1 were used according to the method described in EP-A-0 571 882 prepared method. Table 1: Polyolefin waxes used product type Softening point / dropping point [° C] Viscosity at 170 ° C [mPa · s] Wax 1 (according to the invention) Propylene-ethylene copolymer wax (metallocene) 88 6300 Wax 2 (comparison) Propylene homopolymer wax (metallocene) 143 60 Licowax PP 220 ® (comparative) Propylene homopolymer wax (Ziegler) 158 700
  • Application-technical test results
  • A. Use in hot melt adhesive formulations
  • Using the waxes listed in Table 1, melt adhesive compositions were prepared according to the mixing ratios shown in Table 2. The components were melted together and stirred at 180 ° C for 1 h.
  • To test the cohesion moldings were cast from the mixtures according to DIN 53455 and their mechanical stability was tested in the tensile test.
  • To determine the cold flexibility 250 mm × 10 mm test specimens were prepared and bent over a mandrel. The temperature was lowered in steps of 1 ° beginning at 0 ° C. The measured variable was the temperature at which the test specimen breaks.
  • Figure DE502005008522C5_0006
  • Examples 1 to 3 are according to the invention. By contrast, examples 4 to 9 are comparative examples.
  • Examples 1 to 3 show in comparison with Examples 4 to 6 that by increasing the wax content to greater than 50 wt .-%, a significant improvement in the cohesion and a lowering of the glass transition temperature and an increase in cold flexibility can be achieved. Conventionally, hot-melt adhesive compositions formulated with ethylene-vinyl acetate copolymer and conventional wax show, in addition to higher melt viscosities, comparatively poorer cohesion and, in some cases, poorer cold flexibility (Examples 7 to 9).
  • B. Use as a binder component for road marking
  • Example 10 (Comparative Example)
  • 40 parts by weight Vestoplast ® 708 (APAO, Degussa AG), 40 parts by weight of Regalite ® 1125 (hydrocarbon resin, Eastman), 4 parts by weight of paraffin oil, 12 parts by weight of Licowax ® PP 230 (Ziegler-PP wax from Clariant AG) and 4 parts by weight Licomont ® AR 504 (grafted with maleic anhydride, PP-wax for improving adhesion, Clariant AG) were homogeneously mixed at 180 ° C. 50 g of the obtained melt was spread on a 10 cm × 10 cm pattern pavement of asphalt pavement. After cooling, the coated plate was stored at -15 ° C for 24 hours.
  • Example 11 (according to the invention)
  • A homogenized at 180 ° C melt mixture of 39 parts by weight of the mentioned in Table 1 wax 1 and 9 parts by weight of the mentioned in Table 1 wax 2, 40 parts by weight Regalite ® 1125 and 12 parts by weight Licowax ® PP 230 was used in the manner described in Example 10 to prepare a test coat. The coated plate was again stored at -15 ° C for 24 h.
  • After completion of the cold storage, the plates were removed from the refrigerator. When attempting to detach the test layer manually from the substrate, it was found that the mixture from Example 11 had a significantly better adhesion than the comparison mixture from Example 10.

Claims (10)

  1. Hot melt compositions comprising one or more polyolefin waxes prepared by means of metallocene catalysts, a dropping or softening point ring / ball between 80 and 165 ° C, a melt viscosity, measured at a temperature of 170 ° C, between 20 and 40,000 mPa · s and have a glass transition temperature of at most -10 ° C, characterized in that the polyolefin waxes are contained in a proportion by weight of greater than or equal to 50 wt .-% in the hotmelt, wherein in the hotmelt compositions, the one or more polyolefin waxes are copolymer waxes of propylene and ethylene and the content of structural units derived from propylene in the copolymer waxes is from 70 to 99.9% by weight.
  2. Hot melt compositions according to claim 1, characterized in that the one or more polyolefin waxes a drop or softening point ring / ball between 90 and 160 ° C, a melt viscosity, measured at a temperature of 170 ° C, between 50 and 30,000 mPa · s and have a glass transition temperature of -20 ° C maximum.
  3. Hot melt compositions according to claim 1 or 2, characterized in that the one or more polyolefin waxes have a number average molecular weight M n between 500 and 20,000 g / mol and a weight average molecular weight M w between 1000 and 40,000 g / mol.
  4. Hot melt compositions according to one or more of claims 1 to 3, characterized in that they further contain one or more substances selected from polyolefin plastics, resins, waxes, plasticizers, polar or non-polar polymers, pigments, fillers, stabilizers and antioxidants.
  5. Use of hot melt compositions according to one or more of claims 1 to 4 as hot melt adhesive.
  6. Use according to claim 5, characterized in that the polyolefin waxes are contained in the hot melt compositions in proportions between 50 and 99 wt .-%.
  7. Use according to claim 5, characterized in that the polyolefin waxes are contained in the hot melt compositions in proportions between 60 and 90 wt .-%.
  8. Use of hot melt compositions according to one or more of claims 1 to 4 as binders for the production of road markings.
  9. Use according to claim 8, characterized in that the polyolefin waxes in the hot melt compositions in proportions between 50 and 99 wt .-% are included.
  10. Use according to claim 8, characterized in that the polyolefin waxes are contained in the hot melt compositions in proportions between 60 and 90 wt .-%.
DE502005008522.1T 2004-10-06 2005-09-27 Use of polyolefin waxes in hotmelt compositions Active DE502005008522C5 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE102004048536 2004-10-06
DE102004048536A DE102004048536B4 (en) 2004-10-06 2004-10-06 Use of hot melt compounds in road markings

Publications (2)

Publication Number Publication Date
DE502005008522D1 DE502005008522D1 (en) 2009-12-31
DE502005008522C5 true DE502005008522C5 (en) 2016-10-13

Family

ID=35583523

Family Applications (2)

Application Number Title Priority Date Filing Date
DE102004048536A Active DE102004048536B4 (en) 2004-10-06 2004-10-06 Use of hot melt compounds in road markings
DE502005008522.1T Active DE502005008522C5 (en) 2004-10-06 2005-09-27 Use of polyolefin waxes in hotmelt compositions

Family Applications Before (1)

Application Number Title Priority Date Filing Date
DE102004048536A Active DE102004048536B4 (en) 2004-10-06 2004-10-06 Use of hot melt compounds in road markings

Country Status (5)

Country Link
US (2) US20060074171A1 (en)
EP (1) EP1645608B1 (en)
JP (1) JP5144008B2 (en)
DE (2) DE102004048536B4 (en)
ES (1) ES2334035T3 (en)

Families Citing this family (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8404079B1 (en) 2004-08-09 2013-03-26 H.N. Fuller Company Composition and method relating to a hot melt adhesive
DE102004048536B4 (en) * 2004-10-06 2008-09-18 Clariant Produkte (Deutschland) Gmbh Use of hot melt compounds in road markings
DE102005050996A1 (en) * 2005-10-25 2007-04-26 Clariant Produkte (Deutschland) Gmbh Copolymer for, e.g. paper coating composition, contains at least two monomers from (meth)acrylic esters, unsaturated acids, styrene or its derivatives, di- or trifunctional unsaturated compounds, vinyl ethers, and polymerizable waxes
DE102005055020A1 (en) * 2005-11-18 2007-05-24 Clariant Produkte (Deutschland) Gmbh Use of polyolefin waxes in hotmelt compositions
DE102005055019A1 (en) * 2005-11-18 2007-05-24 Clariant Produkte (Deutschland) Gmbh Use of polyolefin waxes in hotmelt compositions
DE102005055018A1 (en) * 2005-11-18 2007-05-24 Clariant Produkte (Deutschland) Gmbh Use of polyolefin waxes in hotmelt compositions
TWM301820U (en) * 2006-04-25 2006-12-01 Link Treasure Ltd Framework structure of a baby carriage
WO2007131958A1 (en) * 2006-05-17 2007-11-22 Clariant International Ltd Use of propylene copolymer waxes for production of tacky plastics films
CN109320664A (en) * 2006-06-15 2019-02-12 陶氏环球技术有限责任公司 Functionalized olefin interpolymers, composition and the product being made from it and its preparation method
DE102006049089A1 (en) 2006-10-18 2008-04-30 Clariant International Limited Hotmelt
DE102006049090A1 (en) * 2006-10-18 2008-04-30 Clariant International Limited Uploaded adhesive composition through the use of metallocene waxes
EP2125149A2 (en) 2007-02-23 2009-12-02 Donaldson Company, Inc. Formed filter element
US8475621B2 (en) 2007-04-24 2013-07-02 Honeywell International Inc. Adhesion promotion to difficult substrates for hot melt adhesives
DE102007022118A1 (en) * 2007-05-11 2008-11-13 Clariant International Limited Metallocene catalyzed polyolefins in wax formulations and their use for the investment casting / investment casting process
DE102007031967A1 (en) 2007-07-10 2009-01-15 Clariant International Limited Polyolefin-based building materials
DE102007036792A1 (en) * 2007-08-03 2009-02-05 Clariant International Limited Highly crystalline polypropylene waxes
DE102007052965A1 (en) * 2007-11-07 2009-05-14 Clariant International Limited Casting compositions containing waxes especially based on metallocene-catalyzed polyolefins, in particular for the encapsulation of electronic devices and components
DE102007054614A1 (en) * 2007-11-15 2009-05-20 Clariant International Ltd. Wax and polymer formulations containing metallocene-catalyzed polyolefins with and without filler, which are particularly suitable for cutting model production processes and their use for precision casting processes, hollow core production especially in the dental, jewelry and precision engineering sector
DE102007056533A1 (en) * 2007-11-23 2009-05-28 Clariant International Limited Waxy ionomers
DE102007056440A1 (en) * 2007-11-23 2009-05-28 Clariant International Limited Ionomers of poly-1-olefin waxes
DE102007062514A1 (en) * 2007-12-20 2009-06-25 Aksys Gmbh Hot-melt adhesive for bonding a sound-deadening material to a thermoplastic surface comprises an amorphous poly-alpha-olefin, a resin and a filler
US8431642B2 (en) * 2008-06-09 2013-04-30 Exxonmobil Chemical Patents Inc. Polyolefin adhesive compositions and articles made therefrom
US8283400B2 (en) * 2008-06-09 2012-10-09 Exxonmobil Chemical Patents Inc. Polyolefin adhesive compositions
US8242198B2 (en) * 2008-06-09 2012-08-14 Exxonmobil Chemical Patents Inc. Polyolefin adhesive compositions
US8022154B2 (en) * 2008-11-06 2011-09-20 Exxonmobil Chemical Patents Inc. Ethylene polymers, their production and use
US8119549B2 (en) * 2009-01-27 2012-02-21 Milliken & Company Consolidated fibrous structure
US7960024B2 (en) 2009-01-27 2011-06-14 Milliken & Company Multi-layered fiber
US8147957B2 (en) * 2009-01-27 2012-04-03 Milliken & Company Consolidated fibrous structure
US8029633B2 (en) * 2009-01-27 2011-10-04 Milliken & Company Method of forming a consolidated fibrous structure
US8114507B2 (en) * 2009-01-27 2012-02-14 Milliken & Company Multi-layered fiber
US8431643B2 (en) * 2009-05-29 2013-04-30 Exxonmobil Chemical Patents Inc. Polyolefin adhesive compositions and method of making thereof
EP2290029A1 (en) * 2009-08-26 2011-03-02 Sika Technology AG Hot melt adhesives with improved adhesion to low energy surfaces
WO2011059431A1 (en) * 2009-11-11 2011-05-19 Exxonmobil Chemical Patents Inc. Polyolefin adhesive compositions
EP2648507A1 (en) 2010-12-07 2013-10-16 Sanitized AG Method for the antimicrobial treatment of woven fabrics with hot-melt adhesive compositions, hot-melt adhesive compositions and use thereof
EP2666837B1 (en) * 2011-01-18 2017-05-17 Mitsui Chemicals, Inc. Adhesive resin composition and hot-melt adhesive obtained therefrom
RU2467970C1 (en) * 2011-04-22 2012-11-27 Елена Александровна Панова Composition for making monolithic thermoplate as substitute for flexible reinforced primer interlayer or pre-stressed reinforced concrete slabs
JP5850683B2 (en) 2011-09-16 2016-02-03 ヘンケルジャパン株式会社 Hot melt adhesive
JP5850682B2 (en) 2011-09-16 2016-02-03 ヘンケルジャパン株式会社 Hot melt adhesive
JP5924894B2 (en) 2011-09-16 2016-05-25 ヘンケルジャパン株式会社 Hot melt adhesive for disposable products
MX340578B (en) * 2011-09-22 2016-07-13 Flint Trading Inc Anti-skid high retroreflectivity preformed thermoplastic composites for runway applications.
JP5947153B2 (en) * 2012-08-28 2016-07-06 ヘンケルジャパン株式会社 Hot melt adhesive
DE102013005089A1 (en) 2013-03-23 2014-09-25 Clariant International Ltd. Ready-to-use hot-melt adhesive with improved property profile
CN103864983B (en) * 2014-03-14 2016-01-20 保定维特瑞交通设施工程有限责任公司 Based on the heat fusing traffic marking material and preparation method thereof of electro-nic message transmissions

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3679626A (en) * 1966-07-21 1972-07-25 Nippon Paint Co Ltd Thermoplastic traffic paints and process for the manufacture thereof
DE2361055C3 (en) * 1973-12-07 1978-05-11 Hoechst Ag, 6000 Frankfurt
DE3904468A1 (en) * 1989-02-15 1990-08-16 Hoechst Ag Polypropylene wax and process for its manufacture
ES2100388T3 (en) 1992-05-26 1997-06-16 Hoechst Ag Process for preparing polyolefin waxes.
TW322495B (en) 1992-12-15 1997-12-11 Hoechst Ag
DE4446923A1 (en) * 1994-12-28 1996-07-04 Hoechst Ag polyolefin
DE19648895A1 (en) * 1996-11-26 1998-05-28 Clariant Gmbh Polar-modified polypropylene waxes
ES2209008T3 (en) 1997-07-11 2004-06-16 Clariant Gmbh Procedure for oxidation of polyethylene waxes.
EP0890619B1 (en) * 1997-07-11 2004-10-27 Clariant GmbH Use of polyolefinwaxes
DE19729833A1 (en) * 1997-07-11 1999-01-14 Clariant Gmbh polypropylene wax
CN1406267A (en) * 2000-03-01 2003-03-26 科莱恩有限公司 Waves for producing printing inks
US6653385B2 (en) * 2001-10-18 2003-11-25 Bostik Findley, Inc. Hot melt adhesive composition based on a blend of amorphous poly-α-olefin and syndiotactic polypropylene
DE10159955A1 (en) * 2001-12-06 2003-06-26 Clariant Gmbh Use of polar modified polyolefin waxes in photo toners
DE10323617A1 (en) * 2003-05-26 2004-12-23 Clariant Gmbh Melt adhesives
DE10338344A1 (en) * 2003-08-21 2005-03-24 Clariant Gmbh Modified polyolefin waxes
DE102004030714A1 (en) * 2004-06-25 2006-01-12 Clariant Gmbh Melt adhesives
DE102004035837A1 (en) * 2004-07-23 2006-02-16 Clariant Gmbh Use of polyolefin waxes in polycondensates
US7354812B2 (en) * 2004-09-01 2008-04-08 Micron Technology, Inc. Multiple-depth STI trenches in integrated circuit fabrication
DE102004048536B4 (en) 2004-10-06 2008-09-18 Clariant Produkte (Deutschland) Gmbh Use of hot melt compounds in road markings

Also Published As

Publication number Publication date
US7825186B2 (en) 2010-11-02
JP5144008B2 (en) 2013-02-13
EP1645608A1 (en) 2006-04-12
EP1645608B1 (en) 2009-11-18
JP2006104472A (en) 2006-04-20
US20060074171A1 (en) 2006-04-06
ES2334035T3 (en) 2010-03-04
US20080262148A1 (en) 2008-10-23
DE102004048536A1 (en) 2006-04-13
DE102004048536B4 (en) 2008-09-18
DE502005008522D1 (en) 2009-12-31

Similar Documents

Publication Publication Date Title
US7999039B2 (en) High melt strength polymers and method of making same
CN101838362B (en) Polyolefin adhesive compositions and articles made therefrom
CN1130388C (en) Process for synthesizing polyethylene in dual reactor by using phosphinimine catalyst
CN1106426C (en) LLDPE bends with an ethylene-norbornene copolymer for resins of improved toughness and processibility for film production
US6627723B2 (en) Adhesive alpha-olefin inter-polymers
CA2393173C (en) Hot melt adhesive based on blends of epr and/or epdm and semicrystalline olefinic polymers
US5652308A (en) Tackifiers and a process to obtain tackifiers
CA2260954C (en) Hot melt adhesives
CN100448925C (en) Polyethylene pipe resins
US20070135563A1 (en) Adhesives comprising olefin copolymers
US6344515B1 (en) Compositions comprising a substantially random interpolymer of at least one α-olefin and at least one vinylidene aromatic monomer or hindered aliphatic vinylidene monomer
AU733854B2 (en) Hot-melt adhesive composition
EP1330490B1 (en) Polyethylene pipe resins and production thereof
FI112663B (en) Elastic, substantially linear olefin polymers
CA2112021C (en) Polypropylene composition
CN100588663C (en) Multiple catalyst system for olefin polymerization and polymers produced therefrom
CN1231535C (en) Very low density polyethylene blends
US6992131B2 (en) Adhesives
US9353296B2 (en) Adhesive propylene polymer composition suitable for extrusion coating of paper substrates
KR101135405B1 (en) Polymer blends
JP4728643B2 (en) Liquid and gel-like low molecular weight ethylene polymers
US5530054A (en) Elastomeric ethylene copolymers for hot melt adhesives
US5516848A (en) Process to produce thermoplastic elastomers
TWI359155B (en) Hotmelt adhesives
US5548014A (en) Blends of ethylene copolymers for hot melt adhesives

Legal Events

Date Code Title Description
8364 No opposition during term of opposition